Greener Solvent Alternatives

Greener Solvent Alternatives

Supporting the Advancement of Chemistry through Sound Environmental, Social & Fiscal Responsibilities

Green Chemistry

The aim of green chemistry is to reduce chemical related impact on human health and virtually eliminate contamination of the environment through dedicated, sustainable prevention programs. Green chemistry searches for alternative, environmentally friendly reaction media and at the same time strives to increase reaction rates and lower reaction temperatures.

The green chemistry concept applies innovative scientific solutions to solve environmental issues posed in the laboratory. Paul T. Anastas, an organic chemist working in the Office of Pollution Prevention and Toxins at the EPA, and John C. Warner developed the Twelve Principles of Green Chemistry in 1991. These principles can be grouped into Reducing Risk and Minimizing the Environmental Footprint.

2-Methyltetrahydrofuran (2-MeTHF)

CAS No.: 96-47-9

A Truly Green Alternative to Dichloromethane and Tetrahydrofuran

2-MeTHF is derived from renewable resources such as corncobs and bagasse. When used as an organometallic solvent, 2-MeTHF offers both economical and environmentally friendly advantages over Tetrahydrofuran.

Features & Benefits

? Lower peroxide formation than THF (stabilizer required) ? Aprotic polar solvent

? Resembles Toluene in physical properties ? Bromo and lodo Grignards tend to be more soluble in 2-MeTHF

where as chloro Grignard reagents tend to be less soluble

? Forms an azeotrope rich with water

? Can be more easily dried than THF or DCM

? Limited miscibility in water (14g/100g at 23?C)

? Easy separation and recovery from water reduces the waste stream

? Higher boiling point (80?C) compared to THF

? Higher reaction temperature reduces overall reaction time

? Low heat vaporization ? Less solvent loss during reaction refl ux ? Saves energy during distillation and recovery

Alternative to Tetrahydrofuran for organometallic reactions

? Grignard ? Reformatskii (Reformatsky) ? Lithiation ? Hydride Reduction ? Metal-Catalyzed Coupling (Heck, Stille, Suzuki)

CH3

Alternative to Dichloromethane for biphasic reactions

? Alkylation ? Amidation ? Nucleophilic Substitution Reaction

Cat. No.

414247-100mL 414247-1L 414247-6x1L 414247-2L 414247-4x2L 414247-200L-P2

673277-100mL 673277-12x100mL 673277-1L 673277-200L-P2

155810-100mL 155810-12x100mL 155810-500mL 155810-4x4L 155810-20L

2-Methyltetrahydrofuran

Anhydrous, 99.0% Contains 250 ppm BHT

Anhydrous, 99.0% Inhibitor-free

ReagentPlus?, 99.5% Contains 150-400 ppm BHT

Looking to reduce the number of glass bottles in your lab? For more information on our Returnable Containers Program, visit us at

rc

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Greener Solvent Alternatives

Cyclopentyl methyl ether (CPME)

CAS No.: 5614-37-9

Environmentally Friendly Alternative to Tetrahydrofuran, tert-Butyl methyl ether (MTBE), 1,4 Dioxane and other ether solvents

CPME provides a green solution for those looking to improve their chemical process by not only minimizing the solvent waste stream, but also improves laboratory safety due to CPME's unique composition which resists the formation of peroxides.

Features & Benefits

? More stable than THF and 2-MeTHF (stabilizer required)

? Resists peroxide formation ? Reduces the frequency of peroxide testing

? Novel hydrophobic ether solvent

? Useful in many organometallic reactions ? Provides better yields and higher selectivity over THF

? Forms an azeotrope rich with water

? Can be more easily dried than THF and 2-MeTHF

? Limited miscibility in water (1.1g/100g at 23?C)

? Easy separation and recovery from water reduces the waste stream

? Higher boiling point (106?C) compared to THF and

2-MeTHF ? Higher reaction temperature reduces overall

reaction time

? Low heat vaporization

? Less solvent loss during reaction reflux ? Saves energy during distillation and recovery

CPME applications Higher optical purity or selectivity were observed

? Asymmetric Michael Alkylation ? Michael addition of R2CuLi ? Alkylation of chiral amide ? Glycosidation ? Asymmetric hydrogenation of NaBH4 ? Hydrosilylation by Ru cat

OCH3

Nucleophilic reactions

? Amide synthesis by the reaction of acid chloride with amine ? Sillylation and desillylation ? Reaction of Carbon anion with aldehyde ? Debenzylation ? Alkylation of amine ? Selective methylation of phenols ? Bromination of alcohol with PBr3 ? Sulfonylchloride synthesis by the reaction of sulfonic acid with PCl5

Reactions using metals

? Reaction of ketone using NaBH4 ? Reaction of acetylenes with Ti(OR)4 ? Reaction using n-BuLi or Lithium Diisopropyl Amide ? Radical cyclization of trichloroacetate using Cu cat ? Reduction of ethyl benzoate using Lithium

Aluminium Hydride

? Formation of sodium dispersion ? Intramolecular ene reaction using ZnCl2

Cat. No.

675970-100mL 675970-1L 675970-2L

675989-500mL 675989-1L 675989-4L

Cyclopentyl methyl ether

Anhydrous, 99.0% Contains 50 ppm BHT

ReagentPlus?, 99.9% Contains 50 ppm BHT

CPME is a proven alternative to THF, providing better yields and higher selectivity.

Check out the new Spec Comparison page to find the perfect Sigma-Aldrich solvent for your application.

solvents

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Physical Properties of Solvents

Properties

CPME

2-MeTHF

THF

Ether

DCM

1,4-Dioxane

MTBE

Density (20 ?C) [g/cm3]

0.86

0.86

0.89

0.71

1.32

1.03

0.74

Dielectric constant (25 ?C)

250 4.76

6.97

7.58

4.197

8.93

2.227

--

Boiling point [?C]

106

25800

65

34.6

39.8

101

55

Heat of Vaporization (bp) [Kcal/kg]

200 69.2

87.1

98.1 250

86.1

80.5

98.6

81.7

Peroxide wt. ppm Peroxide wt. ppm

Peroxide wt. ppm Peroxide wt. ppm

250 Solubility of Solvent in Water (23 ?C)

Solubility of Water in Solvent 200 (23 ?C)

Azeotropic temperature with Water [?C]

150 Flash point [?C]

Explosion range [vol%] Lower / Upper limit

100

250

1.1

150

0.3 200

100

83

150

?1

50

1.1% / 9.9%

100

200

14

4.4

150

89 ?10101.1

--

50

Infinite

6.5

200

Infinite

1.2

64 150 ?14.2 1.84% / 11.8%100

34 ?45 1.85% / 48%

1.3 0.2 39 -- 14% / 22%

Infinite Infinite

88 12 2% / 22%

4.8 1.5 52 ?28 1.6% / 15.1%

Peroxide wt. ppm

0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 5106 17 18 19 20 21 22 23 24 25 26 27 28 29 30

50 Peroxide Formation of Ether Solv5e0nt

0

Days (x)

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

250 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

CPME Stabilized

THF0 Stabilized DayTsHT(HxF)F19 days to reach 100 ppm

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

5Da6ys 7(x)8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 025 26 27 28 29 30

0

0

1200 2

3

R4 aDt5eayo6sf(x7P)e8rox9id10e

Formation by

11 12 13 14 15 16

d0ay1s 17 18

(2x) 19

3 20

4 21

5 22

THF Stabilized

YT=H1F5.277e0.0962x + 12D.9apysp(mx)

6 23

7 24

8 25

9 10 1C1PM12E 1S3ta1b4 ili1z5ed16

26 27 28 29 30

Days (x)

17

18

19THT20HFF21SSt2aa2bbi2li3ilzize24edd25120622d7Da2y8yTssH2(9Ftxo)30reach 100 ppm CCPPMME SSttaabbilizliezded 683 daTyHsFtoStarebailiczhed100 ppm THF

CPME Stabilized

150

YT=HF0.S8ta2b1i8lixze+d15.9 ppm THF YCP=M0E.1S3ta9b7ixliz+e4d.5 ppm THF Stabilized

CPTMHEF Stabilized

THF Stabilized

THF

Conditions

Peroxide wt. ppm

? 20 mL of each sample in a brown bottle

100

(capacity of 65 mL)

? Stored at room temperature, in a dark place

and in the presence of air

50

0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Days (x)

CPME is a product of Zeon Corporation with approval by Toxic Substances Control Act (TSCA) and European List of Notified Chemical Substances (ELINCS).

CPME Stabilized

THF Stabilized

THF

Enabling Science to Improve the Quality of Life

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Development/Custom Manufacturing Inquiries

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Safety-related Information: safetycenter

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